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Enhanced dielectricity coupled to spin-crossover in a one-dimensional polymer iron(ii) incorporating tetrathiafulvalene.


ABSTRACT: In designing multifunctional materials for potential switches that can be used as memory devices, the high-spin (HS) to low-spin (LS) crossover (SCO) one-dimensional polymer, [FeII(L)(4,4'-bpy)] n , was constructed from a designed redox-active tetrathiafulvalene (TTF) functionalized Schiff-base and the ditopic linker 4,4'-bipyridine (bpy). It exhibits an 8 K hysteretic SCO centred at T 1/2 = 325 K which is coupled to changes in its dielectric constant. The crystal structures above and below the transition temperature reveal similar parallel linear ···Fe-bpy-Fe-bpy··· chains displaying expansion of the FeII octahedron in the HS state. Density functional theory (DFT) calculations reveal a concerted electronic charge and spin change represented by the Mülliken charge of the Fe and the magnitude and direction of the dipole moment which substantiate the experimental observations.

SUBMITTER: Qiu YR 

PROVIDER: S-EPMC7480181 | biostudies-literature | 2020 Jun

REPOSITORIES: biostudies-literature

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Enhanced dielectricity coupled to spin-crossover in a one-dimensional polymer iron(ii) incorporating tetrathiafulvalene.

Qiu Ya-Ru YR   Cui Long L   Cai Pei-Yu PY   Yu Fei F   Kurmoo Mohamedally M   Leong Chanel F CF   D'Alessandro Deanna M DM   Zuo Jing-Lin JL  

Chemical science 20200527 24


In designing multifunctional materials for potential switches that can be used as memory devices, the high-spin (HS) to low-spin (LS) crossover (SCO) one-dimensional polymer, [Fe<sup>II</sup>(L)(4,4'-bpy)] <sub><i>n</i></sub> , was constructed from a designed redox-active tetrathiafulvalene (TTF) functionalized Schiff-base and the ditopic linker 4,4'-bipyridine (bpy). It exhibits an 8 K hysteretic SCO centred at <i>T</i> <sub>1/2</sub> = 325 K which is coupled to changes in its dielectric consta  ...[more]

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